Quick-setting mixtures and kits with polyfunctional cyanates and amines, the thermosets produced therefrom and methods for the production thereof

ABSTRACT

The invention describes a fast curable system for the preparation of amine modified thermosettings containing triazine groups, the system comprising at least one polyfuctional organic monomeric or prepolymerized cyanate and at least one primary or secondary amine, wherein the amount of amine is selected such that the molar ratio of cyanate radicals to amine radicals is from 95:5 to 50:50, and optionally additional additives, characterized in that the amine is present in a form having a blocked or decreased reactivity which can be reactivated without reacting it with a chemical participant of reaction. Further, it is directed to amine modified thermosetting materials containing triazine groups as well as to a method for preparing same.

FIELD OF THE INVENTION

This invention is directed to fast curable polymers of polycyanates andpolycyanate/epoxide combinations together with amine curing agents.These polymers are widely useful, specifically as laminating resins,adhesives, casting resins, underfillers, masking or encapsulatingagents, coating agents. They have a high thermostability, they arefire-retardant, and their pot life and processing temperature iscontrollable in broad ranges.

DESCRIPTION OF THE RELATED ART

Thermosetting materials made of polycyanates (polyfunctional cyanic acidesters of the general formula R(OCN)_(n)) are increasingly used,specifically as laminating resins and adhesives in the high-tech area(for a review see e.g. “Chemistry and Technology of Cyanate EsterResins”, I. Hamerton (ed.), Chapman & Hall, Glasgow, 1994). They arespecifically characterized by high glass transition temperatures anddecomposition temperatures, flame-resistance even without the additionof nonflammable additives, high viscosity compared to other thermosetshaving high glass transition temperatures, low dielectric losses, goodadhesion to a multiplicity of substrate materials, high chemicalresistance and a low corrosiveness.

The curing reaction of polycyanates (polycyclotrimerization topolycyanurates) is rather slow in case very pure monomers are used.Impurities resulting from the monomer synthesis, e.g. unreacted phenolsor water, catalyze the curing reaction, but in an undefined anduncontrollable way. For this reason, very pure monomers are used, someof which are commercially available, e.g. AroCy B-10 based on BisphenolA of Lonza AG, Schweiz. To accelerate the curing reaction andconsequently to obtain more efficient methods for the manufacture ofpolycyanates, a variety of catalysts is used. For this purpose,especially metal acetylacetonates, zinc salts, a variety oforganometallic compounds as well as phenols, and compounds containing NHradicals have successfully been used.

As known since the sixties, primary and secondary amines easily reactwith cyanates (see e.g. Grigat, E. et al., Angew. Chem. 79, 219 (1967)).Consequently, it has been attempted to use amines as catalysts for thecyclotrimerization of cyanates. As a result, however, the reactivity ofthe mixture is too high and the processing is not under control,especially when aliphatic amines arc used, e.g. common epoxide curingagents. Thus, the dicyanate AroCy® L-10 (Lonza AG) which is liquid atroom temperature, abruptly turns into a gelled condition immediately assoon as a low amount of diaminohexane is admixed thereto. In contrast,by use of solid amine powder in combination with other solid catalysts(0.1-1.5 wt.-%), the formulation of a cyanate/epoxy system useful as anunderfiller (U.S. Pat. No. 5,855,821) is obtained, wherein the amine isnot catalytically active until an increased curing temperature isreached.

If molar amounts of an amine are used which exceed 1 mol-%, relative tothe cyanate radicals, it cannot be said that the action is merelycatalytic. Instead, a co-reaction between cyanate and amine occurs bywhich the amount of the cyanaruate structures obtained solely from thecyanates drastically decreases. This reaction has already been used forthe production of curable polyaddition products (see e.g. DE 12 20 132).In this case, solutions of the amine and the cyanate were mixed, thepolyadduct was separated in substance, and this mass was cured at anelevated temperature. Use of bifunctional educts yielded linear productswhich were linked by isourea ether groups. If trifunctional ormultifunctional amines and/or trifunctional and multifunctional cyanatesare solely used or used in addition, respective cross-linked plasticsshould be obtained.

Pre-produced polymer adducts of cyanates and amines are also useful forthe production of thermoresistant thermosets, if they are mixed withother reactive resins, e.g. maleimides (U.S. Pat. Nos. 4,499,245,4,370,467), cyclopentadienes (U.S. Pat. No. 4,469,859), polyhydantoins(U.S. Pat. No. 4,410,666), polyisocyanates (U.S. Pat. No. 4,369,302),epoxies (U.S. Pat. No. 4,393,195, EP 0,369,527) und others.

Since the presence of a larger amount of amine in a mixture of a cyanateand an amine should necessarily result in an uncontrollable productionof acyclic or cross-linked polycyanates, the co-polymerization of alarger amount of an amine with a polyfunctional cyanate does not seem apossible route in order to arrive at the production of modifiedpolycyanurates.

BRIEF SUMMARY OF THE INVENTION

It is an object of the present invention to provide resin systems madeof polyfunctional cyanates or mixtures of cyanates and epoxides togetherwith amines which may be reacted to thermosetting polycyanate copolymershaving a high proportion of triazine structures, as well as to providethermosetting plastics thus obtained. Further, it is an object of thepresent invention to provide resin systems from which the saidthermosetting polycyanates may be obtained by applying short curingtimes and in high reproducibility.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

FIG. 1 shows an IR spectrum in an embodiment according to the presentinvention.

FIG. 2 shows a differential thermogram in an embodiment according to thepresent invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

It has been found that combinations of cyanates or mixtures of cyanatesand epoxides, respectively, and amines may be formulated which allow fora controllable curing without the necessity of a previousprepolymerization. In this formulations, molar ratios of amino radicalsof from about 5 to about 50 mol-% may be used, relating to the sum ofthe amino and the cyanate radicals present in the mixture, which allowsfor a wide variety of gelling and curing times. This is obtained by theaddition of primary or secondary amines the reactivity of which isblocked or decreased, and especially which are chemically or physicallyencapsulated, to the cyanates or mixtures of cyanates and epoxides,respectively. After liberation of the amine, e.g. by melting it atincreased temperatures, by removing sheath or coatings, by the action ofpressure or of supersonic waves or of other energy types, the curingreaction of the resins starts. Curing times may be between a few secondsand some hours, depending on the composition of the resin, thereactivity of the amine and the curing temperature. The glass transitiontemperatures of the cured thermosets may vary in relation to thestructure of the basic cyanate/epoxide resins used and often are between120° C. and 350° C. High glass transition temperatures are specificallyobtained in case novolak cyanates or novolak epoxides are used. Veryshort curing times are attained when primary alkyl amines are used.

The cyanates to be used according to the invention may be polyfunctionalcyanates, and preferably those having the following structures I-IV:

wherein R¹ to R⁴ are independently from each other hydrogen,C₁-C₁₀alkyl, C₃-C₈ cycloalkyl, C₁-C₁₀ alkoxy, halogen, phenyl orphenoxy, the alkyl or aryl groups optionally being partly or fullyfluorinated. Examples are phenylene-1,3-dicyanate,phenylene-1,4-dicyanate, 2,4,5-trifluorophenylene-1,3-dicyanate;

wherein R⁵ to R⁸ are as R¹ bis R⁴ and Z is a chemical bond, SO₂, CF₂,CH₂, CHF, CH(CH₃), isopropyl, hexafluoroisopropyl, C₁-C₁₀ alkyl, O, NR⁹,N═N, CH═CH, COO, CH═N, CH═N—N═CH, alkyloxyalkyl having a C₁-C₈ alkylgroup, S, Si(CH₃)₂ or

Examples are 2,2-bis(4-cyanato-phenyl)propane,2,2-bis(4-cyanato-phenyl)hexafluoropropane, biphenylene4,4′-dicyanate;

wherein R⁹ is hydrogen or C₁-C₁₀ alkyl and n is an integer from 0 to 20,as well as

N≡C—O—R¹⁰—O—C≡N  IV

wherein R¹⁰ is a two-binding organic non-aromatic hydrocarbon having atleast one fluorine atom and preferably 3 to 12 carbon atoms. The saidcyanates may be used as monomers or prepolymers, alone or in mixturewith each other or in mixture with other monofunctional orpolyfunctional cyanates.

The properties of the polycyanurate resins obtainable therefrom, andespecially the glass transition temperatures, may be manipulated e.g. byway of copolymerization of the polyfunctional cyanates and/or theirprepolymers with monocyanates having the structures V or VI, wherein R¹to R⁵ and R¹⁰ are as previously defined, the amount of cyanate radicalsof monofunctional cyanates being up to 50 mol-%, in relation to allcyanate radicals of the mixture.

N≡C—O—R¹⁰  V

To the mixtures, monofunctional or polyfunctional glycidyl ethers may beadded in amounts up to 75 mol-%, preferably up to 50 mol-%, in relationto the sum of the glycicyl and cyanate radicals.

Glycidyl ethers to be used may have the following basic structure:

wherein R is any aromatic, aliphatic or cycloaliphatic radical and n isfrom 1 to 20. Examples are phenyl glycidyl ether,2,2-bis(4-glycidyloxy-phenyl)propane,bis(glycidyloxy)tetramethyldisiloxane or novolak cyanates having thestructure III, wherein OCN is replaced by a glycidyl ether group—OCH₂(CHCH₂O). The glycidyl ethers may be used as pure substances or asprepolymers.

For solvent-free resin systems, liquid cyanates, e.g. AroCy® L-10 (LonzaAG), or liquid mixtures of AroCy® L-10 in combination with othercyanates or the prepolymers thereof, or liquid mixtures of cyanates andglycidyl ethers, e.g. Rütapox (Bakelite AG), may be used. Alternatively,solvents may be used, for example those which dissolve the cyanates orthe cyanate epoxide combinations, respectively, but do not dissolve theamine the reactivity of which is blocked or decreased. Useful solventsfor such cases are e.g. acetone, dichloromethane, tetrahydrofuran,diethyleneglycol dimethyl or diethyl ether, diethyleneglycol monobutylether acetate.

The definition “primary or secondary amines which show blocked ordecreased reactivity and especially ones which are chemically orphysically encapsulated” shall mean those amines which due to a chemicalor physical blocking are incapable or only have very low capability toreact with cyanate which is present in the same mixture, but mayregenerate their reactivity without reacting with a chemical reactantwhich would cleave a protective group. These properties may be inherentto the amines due to physical or chemical conditions. Particularlysuitable are primary or secondary amines the restoration of reactivityof which is merely performed by increasing the temperature at a time asdesired. For these cases, it is specifically preferred to use amines inparticulate shape which are solid and undissolved or undissolvable atthe storage conditions of the components or the mixture thereof. Uponheating, the amine will melt, thereby regenerating the reactivityimmediately, either by reactions at the grain boundaries or in solution.In another embodiment, finely suspended particles of the amine or theamine mixture are encapsulated, i.e. coated with a protective layer orsheath, so that no free amino radicals are available to the functionalgroups of the resin and in turn no curing reaction may take place beforethe protective sheath is disrupted. The sheath or layer will melt orbreak only upon increased temperature, thereby releasing the previouslycoated amine. This protective sheath may protect solid amines, but insome cases also semisolid or liquid ones, for example if it has theshape of coatings (e.g. made of wax) or of vesicles the membrane ofwhich is unstable at raised temperatures.

In another embodiment of the invention, the amines are chemicallymodified. It is specifically preferred that only the outer shell ofsolid amine particles is treated. This is performed by adding aprotective group to those amine radicals which are in contact with theouter environment. This chemical modification may but need notnecessarily be reversed without a chemical reactant. This is especiallythe case in the preferred embodiment, because only a small part of theamine, depending of the particle size, e.g. about 10% of the amine, isinactivated by the modification. This amount may then be compensated byadding an increased amount of amine, if necessary. Such a modificationmay especially be attained by suspending a solid amine or amine mixturein an e.g. nonpolar solvent and reacting the amino radicals present onthe surface of the particles e.g. with isocyanates and/or chlorosilanes.Amines thus encapsulated are not dissolvable in the resin at lowtemperatures, and no reactions take place. Upon raising the temperatureup to the melting range of the amine or the encapsulating layer,respectively, the sheath or capsule will disintegrate, presenting thepreviously inward amine, and the curing reaction of the resin willstart. The starting temperature may be controlled by the melting range,and the curing time may be controlled by the reactivity of the amine.

The size of the amine particles to be used may be chosen as desired.Preferably, the particles have a diameter of from about 1 to 100 μm,more preferably of <20 μm.

The reactivity of the amines may be restored not only by applying heatas mentioned before, but also by other measurements like change ofpressure, sonification, irradiation or the like. The amount of energieintroduced therewith (e.g. by means of strong mechanical vibrations,e.g. by ultrasound, or by strong shearing forces, e.g. in a mixingapparatus) may result in breaking up the capsule. After releasing, theamines can for example dissolve in the resin without melting, whereuponthe reaction is started. Radiation which is rich of energy, or the likemay optionally be used in order to break a chemical bonding which inturn yields a free amino radical.

The selection of the amines as such is not critical. If solid amineparticles are used which are to melt, it may be performed consideringthe melting point of the amine which in turn should correspond to thetemperature at which the resin is to be cured. The selection of thenumber of amino groups per molecule is made in the light of the desiredproperties of the thermosetting material to be prepared, which is withinthe knowledge of a skilled person. Likewise, primary and/or secondaryamines as well as additional properties are selected. For example, alkylamines, which in principle should be acceptable, might be considered asnot useful because they might have too high a reactivity and/or too lowa melting point (often they are “waxy” which makes encapsulation thereofdifficult). As examples for amines which may successfully be used,1,2-diaminobenzene, 1,3-diaminobenzene, 4,4′-diaminodiphenylsulphone,4,4′-diaminodiphenylmethane, piperazine, 1,4-diaminocyclohexane,α,α′-diamino-p-xylene, or amines having a structural relationship withthese substances, are mentioned.

The ratio between the amount of the cyanate and that of the amine isalso not critical and will preferably be in the range of 95:5 to 50:50,relative to the number of the cyanate and amino groups present.

The polyfunctional cyanates and the prepolymers or mixtures thereof tobe used according to this invention, and the amines useful in theinvention, may optionally be stored separately until it is intended toprepare the thermosetting material. However, due to the specificproperties of the used amines, it is specifically possible to preparemixtures with a long shelf life into which the required amount of aminehas already been incorporated. The expression “having a long shelf life”shall mean a mixture which may be stored at least one or two days, butin many instances as long as some weeks or months, withoutpolymerization taking place which in turn would substantially affect theresult of the later preparation of the thermosetting material.

One-component-systems as well as two-component-systems having pot lifes(so called “pot times” at room temperature) of a few days up to somemonths may be formulated. As soon as the preparation of the thermoset isdesired, the required heat or energy is incorporated into the mixture ofthe components, whereupon spontaneous curing occurs which has beenfinalized after about 1 s and some hours, depending on the reactivity ofthe components selected.

The thermosetting materials thus obtained include one ore more of thefollowing structural elements:

wherein an increasing amount of amine yields the predominant formationof structures C and D. If 20 mol-% amine groups or more are contained,cyanurate structure A can almost not be detected.

In order to formulate adhesives, underfillers, coatings (lacquer, paint)and the like, the resin having the composition as detailed above may becompounded with additives which are generally employed for a respectiveuse, e.g. thixotroping agents, fillers, dyes, conductivity enhancingagents, tougheners, and the like.

The invention shall further be illustrated by the following examples:

EXAMPLE 1

39.6 g of bis-(4-aminophenyl)methane are finely ground in a mill(particle size <20 μm), and the powder thus obtained is suspended in 500ml cyclohexane at 60° C. with vigorous stirring. 17 ml of1,6-diisocyanatohexane are dissolved in 40 ml cyclohexane, and thesolution thus obtained is added dropwise to the amine containingsuspension. After 30 min, the suspension is filtered and the filtrate iswashed with cyclohexane and dried. 40 g of a white powder are obtained.To 9 g AroCy® L-10 (Lonza AG), compound II with R¹-R⁸=H, Z=phenylmethyl,1 g of the encapsulated amine is added, and the mixture is stirred well.A stable opaque suspension forms. After one week at room temperature,the viscosity of the resin is increased by not more than 10%. Thegelling times of the mixture are 1 s at 150° C. and 10 s at 100° C.After 2 min at 150° C., curing of the resin is terminated. Thethermosetting material thus obtained has a glass transition temperatureof 218° C.

EXAMPLE 2

26 g of 1,4-diaminobenzene are finely ground in a mill (particle size<20 μm), and the powder thus obtained is suspended in 320 ml cyclohexaneat 70° C. with vigorous stirring. 11.6 ml 1,6-diisocyanatohexane aredissolved in 65 ml cyclohexane, and the solution thus obtained is addeddropwise to the amine containing suspension. After 10 min, thesuspension is filtered and the filtrate is washed with cyclohexane anddried. 31.3 g of a pale violet powder are obtained. To a mixture of 6.3g AroCy® L-10 (Lonza AG), compound II with R¹-R⁸=H, Z=phenylmethyl, and2.7 g Rütapox 0164 (Bakelite AG), 1 g of the encapsulated amine isadded, and the mixture is stirred well. A stable opaque suspensionforms. After three weeks at room temperature, the viscosity of the resinis increased by not more than 6%. The gelling times of the mixture are30 s at 150° C. and 100 s at 120° C. After 4 min at 150° C., curing ofthe resin is terminated. The thermosetting material thus obtained has aglass transition temperature of 187° C.

EXAMPLE 3

26 g of 1,4-diaminobenzene are finely ground in a mill (particle size<20 μm), and the powder thus obtained is suspended in 320 ml cyclohexaneat 70° C. with vigorous stirring. 11.6 ml 1,6-diisocyanatohexane aredissolved in 65 ml cyclohexane, and the solution thus obtained is addeddropwise to the amine containing suspension. After 10 min, thesuspension is filtered and the filtrate is washed with cyclohexane anddried. 31.3 g of a pale violet powder are obtained. To a mixture of 6 gprepolymer of AroCy® B-10 (Lonza AG), compound II with R¹-R⁸=H,Z=isopropyl, degree of conversion of cyanate radicals 32%, and 3 gbutanediol diglycidyl ether, 1.5 g of the encapsulated amine are added,and the mixture is stirred well. A stable opaque suspension forms. Afterthree weeks at room temperature, the viscosity of the resin is increasedby not more than 4%. The gelling times of the mixture are 15 s at 150°C. and 50 s at 120° C. After 3 min at 150° C., curing of the resin isterminated. The thermosetting material thus obtained has a glasstransition temperature of 164° C.

EXAMPLE 4

24 g of 1,4-diaminobenzene are finely ground in a mill (particle size<20 μm), and the powder thus obtained is suspended in 470 ml cyclohexaneat 70° C. with vigorous stirring. 13.9 ml isophorone diisocyanate aredissolved in 70 ml cyclohexane, and this solution is added dropwise tothe amine containing suspension. After 10 min, the suspension isfiltered and the filtrate is washed with cyclohexane. The powder thusobtained is suspended in 250 ml toluene and 20.5 ml triethylamine at 25°C. with vigorous stirring. 18.9 ml trimethyl chlorosilane are dissolvedin 30 ml toluene, and this solution is added dropwise to the saidsuspension. After 60 min, the suspension is filtered and the filtrate iswashed with toluene and dried. 25.2 g of a pale violet powder areobtained. To a mixture of 6.3 g AroCy® PT-15 (Lonza AG), compound IIIwith R⁹=H, and 2.7 g butanediol diglycidyl ether, 1.2 g of theencapsulated amine are added, and the mixture is stirred well. A stableopaque suspension forms. After two months at room temperature, theviscosity of the resin is increased by not more than 5%. The gellingtimes of the mixture are 10 s at 150° C. and 25 s at 120° C. After 3 minat 150 C., curing of the resin is terminated. The thermosetting thusobtained has a glass transition temperature of 201° C. Attached FIG. 1shows the IR spectrum of a thermoset prepared in the same way, exceptthat the curing time was 5 minutes at 150° C.

EXAMPLE 5

17.1 g of 1,4diaminocyclohexane are finely ground in a mill (particlesize <20 μm), and the powder thus obtained is suspended in 400 mlcyclohexane at 25° C. with vigorous stirring. 6.3 ml isophoronediisocyanate is dissolved in 50 ml cyclohexane, and this solution isadded dropwise to the amine containing suspension. After 15 min, thesuspension is filtered and the filtrate is washed with cyclohexane. Thepowder thus obtained is suspended in 200 ml toluene and 13.7 mltriethylamine at 25° C. with vigorous stirring. 12.6 ml trimethylchlorosilane are dissolved in 30 ml toluene, and the solution is addeddropwise to the said suspension. After 30 min, the suspension isfiltered and the filtrate is washed with toluene and dried. 19.8 g of apale yellow powder are obtained. To a mixture of 5 g AroCy® L-10 (LonzaAG), compound II with R¹-R⁸=H, Z=isopropyl, and 4 g trimethylolpropanetriglycidylether, 1.1 g of the encapsulated amine are added, and themixture is stirred well. A stable opaque suspension forms. After twomonths at room temperature, the viscosity of the resin is increased bynot more than 5%. The gelling times of the mixture are 1 s at 150° C.and 20 s at 80° C. After 60 s at 150 C., or after 5 min at 80° C.,respectively, curing of the resin is terminated. The thermosetting thusobtained has a glass transition temperature of 170° C.

Comparative Example 1

Example 4 was repeated, except that 1,4-diaminobenzene without priorencapsulation was mixed with the resin.

FIG. 2 shows the differential thermogram of the curings of a mixtureaccording to example 4 (graph 1) and a mixture according to comparativeexample 1 (graph 2). The mixture according to example 4 shows nosubstantial curing reaction up to about 100° C. At about 120° C., thereaction almost suddenly starts and is terminated at a temperature ofabout 170° C. at the selected heating rate of 5 K/min. In contrast,curing of the mixture according to comparative example 1 already startsat the beginning of the measurement at 27° C. and is almost completeuntil a temperature of about 120° C. is reached.

We claim:
 1. Fast curable system for the preparation of amine modifiedthermosetting materials containing triazine radicals, comprising: a) atleast one polyfunctional organic monomeric or prepolymerized cyanate andb) at least one primary or secondary amine, wherein the amount of amineis selected such that the molar ratio of cyanate to amine radicals is95:5 to 50:50, characterized in that the amine present has a blocked ordecreased reactivity which can be reactivated without reacting it with achemical participant of reaction.
 2. Fast curable system according toclaim 1, wherein the polyfuctional organic cyanate is selected amongcyanates having formulae I to IV:

wherein R¹ to R⁴ are independently from each other hydrogen, C₁-C₁₀alkyl, C₃-C₈ cycloalkyl, C₁-C₁₀ alkoxy, halogen, phenyl or phenoxy,

wherein R⁵ to R⁸ are as R¹ to R⁴ and Z is a chemical bond, SO₂, CF₂,CH₂, CHF, CH(CH₃), isopropyl, hexafluoroisopropyl, C₁-C₁₀ alkyl O, NR⁹,N═N, CH═CH, COO, CH═N, CH═N—N═CH, alkyl oxyalkyl containing C₁-C₈-Alkyl,S, Si(CH₃)₂,

wherein R⁹ is hydrogen or C₁-C₁₀ alkyl and n is an integer of from 0 to20, N≡C—O—R¹⁰—O—C≡N  IV wherein R¹⁰ is a two-binding organicnon-aromatic hydrocarbon having at least one fluorine as well as amongprepolymers of the said cyanates.
 3. Fast curable system according toclaim 2, wherein the cyanates having structure I are selected amongphenylene-1,3-dicyanate, phenylene-1,4-dicyanate and2,4,5-trifluorophenylene-1,3-dicyanate.
 4. Fast curable system accordingto claim 1, wherein the system additionally contains at least onemonofunctional cyanate selected from those of structure V and VIN≡C—O—R¹⁰  V

and of prepolymers thereof and of prepolymers containing at least onecyanate of formulae V or VI.
 5. Fast curable system according to claim1, wherein the system additionally contains at least one mono- orpolyfunctional glycidyl ether in an amount of up to 7.5 mol-%, glycidylradicals, in relation to the sum of glycidyl radicals and cyanateradicals.
 6. Fast curable system according to claim 5, wherein the mono-or polyfunctional glycidyl ethers are selected among those of thefollowing formula:

wherein R is any aromatic, aliphatic or cycloaliphatic radical, and n isan integer of 1 to
 20. 7. Fast curable system according to claim 5,wherein the glycidyl ethers are selected from the group consisting ofphenyl glycidyl ether, 2,2-bis(4glycidyloxy-phenyl)propane,bis(glycidyloxy)tetramethyldisiloxane and novolak cyanates of structureIII wherein OCN has been replaced by a glycidylether residue—OCH₂(CHCH₂O).
 8. Fast curable system according to claim 1, wherein theamine is in the shape of solid particles which are insoluble in theirenvironment and have a diameter of from 1 to 100 μm.
 9. Fast curablesystem according to claim 5, wherein the amine particles are chemicallyinert at their outer surface.
 10. Fast curable system according to claim9, wherein the outer surface of the amine particles has been reactedwith isocyanates and/or chlorosilanes.
 11. Method for preparing aminemodified thermosetting materials containing triazine groups, wherein atleast one polyfunctional organic monomeric or prepolymerized cyanate andat least one of primary and secondary amines are mixed and reacted, andthe amount of amine is selected such that the molar ratio of cyanateradicals to amine radicals is from 95:5 to 50:50, wherein the cyanate ismixed with the amine while the amine has a blocked or decreasedreactivity which can be reactivated without reacting it with a chemicalparticipant of reaction, and subsequently the amine is reactivated. 12.Method according to claim 11, wherein at least one selected frommonofunctional cyanates and glycidyl ethers is additionally mixed withthe cyanate.
 13. Fast curable system according to claim 1, comprisingadditional additives.
 14. Fast curable system according to claim 2,wherein the alkyl or aryl radicals R¹ to R⁴ in the cyanates of formula Iare fluorinated.
 15. Fast curable system according to claim 2, whereinR¹⁰ of the cyanates of formula IV is a two-binding organic non-aromatichydrocarbon having at least one fluorine atom and 3 to 12 carbon atoms.16. Fast curable system according to claim 2, wherein the cyanates offormula II are selected from 2,2-bis(4-cyanato-phenyl)propane,2,2-bis(4-cyanato-phenyl)hexafluoropropane andbiphenylene-4,4′-dicyanate.
 17. Fast curable system according to claim1, wherein the system additionally contains at least one mono- orpolyfunctional glycidyl ether in an amount up to 50 mol-% glycidylradicals, in relation to the sum of glycidyl radicals and cyanateradicals.
 18. Fast curable system according to claim 8, wherein theamine is in the shape of solid particles which are insoluble in theirenvironment and have an average diameter of <20 μm.